ALD OF AMORPHOUS LANTHANIDE DOPED TiOX FILMS

ABSTRACT

The use of atomic layer deposition (ALD) to form an amorphous dielectric layer of titanium oxide (TiO X ) doped with lanthanide elements, such as samarium, europium, gadolinium, holmium, erbium and thulium, produces a reliable structure for use in a variety of electronic devices. The dielectric structure is formed by depositing titanium oxide by atomic layer deposition onto a substrate surface using precursor chemicals, followed by depositing a layer of a lanthanide dopant, and repeating to form a sequentially deposited interleaved structure. Such a dielectric layer may be used as the gate insulator of a MOSFET, as a capacitor dielectric, or as a tunnel gate insulator in flash memories, because the high dielectric constant (high-k) of the layer provides the functionality of a thinner silicon dioxide layer, and because the reduced leakage current of the dielectric layer when the percentage of the lanthanide element doping is optimized.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This is a divisional of U.S. application Ser. No. 11/737,460 filed Apr.19, 2007, which is a divisional of U.S. application Ser. No. 11/092,072filed Mar. 29, 2005, now U.S. Pat. No. 7,365,027, which applications areincorporated herein by reference in its entirety.

TECHNICAL FIELD

This application relates generally to semiconductor devices and devicefabrication and, more particularly, to dielectric layers and theirmethod of fabrication.

BACKGROUND

The semiconductor device industry has a market driven need to reduce thesize of devices such as transistors. Smaller transistors result inimproved operational speed and clock rate, and reduced powerrequirements in both the standby and operational modes. To reducetransistor size, the thickness of the silicon dioxide (SiO₂) gatedielectric is reduced in proportion to the shrinkage of the gate length.For example, a metal-oxide-semiconductor field effect transistor(MOSFET) might use a 1.5 nm thick SiO₂ gate dielectric for a gate lengthof less than 100 nm. Such thin gate dielectrics are a potentialreliability issue and may be the most difficult issue facing theproduction of the upcoming generations of MOSFETs. The increasinglysmall and reliable integrated circuits (ICs) will likely be used inproducts such as processor chips, mobile telephones, and memory devicessuch as dynamic random access memories (DRAMs).

The semiconductor industry relies on the ability to reduce (or scale)all of the dimensions of its basic devices, such as the silicon basedMOSFET, to achieve improved operational speed and power consumption.Device scaling includes scaling the gate dielectric, which has primarilybeen formed of silicon dioxide (SiO₂). A thermally grown amorphous SiO₂layer provides an electrically and thermodynamically stable material,where the interface of the SiO₂ layer with underlying silicon provides ahigh quality interface as well as superior electrical isolationproperties. However, increased scaling and other requirements inmicroelectronic devices have created reliability issues as the gatedielectric has become thinner. The reliability concerns suggest the useof other dielectric materials as gate dielectrics, particularlymaterials with higher dielectric constants.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an atomic layer deposition system for fabricating adielectric layer formed as a nanolaminate layered sequence of alanthanide and titanium oxide, according to various embodiments of thepresent invention;

FIG. 2 illustrates a flow diagram of elements for an embodiment of amethod to form a dielectric layer containing lanthanide doped titaniumoxide by atomic layer deposition according to various embodiments of thepresent invention;

FIG. 3 illustrates an embodiment of a configuration of a transistorhaving a dielectric layer containing an atomic layer depositedcontaining lanthanide doped titanium oxide, according to the presentinvention;

FIG. 4 shows an embodiment of a configuration of a capacitor having adielectric layer containing an atomic layer deposited lanthanide dopedtitanium oxide, according to the present invention;

FIG. 5 is a simplified diagram for an embodiment of a controller coupledto an electronic device, according to the present invention; and

FIG. 6 illustrates a diagram for an embodiment of an electronic systemhaving devices with a dielectric film containing an atomic layerdeposited layered sequence of lanthanide doped titanium oxide, accordingto the present invention.

DETAILED DESCRIPTION

The following detailed description refers to the accompanying drawingsthat show, by way of illustration, specific aspects and embodiments inwhich the present invention may be practiced. These embodiments aredescribed in sufficient detail to enable those skilled in the art topractice the present invention. Other embodiments may be utilized andstructural, logical, and electrical changes may be made withoutdeparting from the scope of the present invention. The variousembodiments are not necessarily mutually exclusive, as some embodimentscan be combined with one or more other embodiments to form newembodiments.

The terms wafer and substrate used in the following description includeany structure having an exposed surface with which to form an integratedcircuit (IC) structure. The term substrate is understood to includesemiconductor wafers. The term substrate is also used to refer tosemiconductor structures during processing, and may include other layersthat have been fabricated thereupon. Both wafer and substrate includedoped and undoped semiconductors, epitaxial semiconductor layerssupported by a base semiconductor or insulator, as well as othersemiconductor structures well known to one skilled in the art. The termconductor is understood to generally include n-type and p-typesemiconductors, and the term insulator or dielectric is defined toinclude any material that is less electrically conductive than thematerials referred to as conductors or as semiconductors.

The term “horizontal” as used in this application is defined as a planeparallel to the conventional plane or surface of a wafer or substrate,regardless of the orientation of the wafer or substrate. The term“vertical” refers to a direction perpendicular to the horizontal asdefined above. Prepositions, such as “on”, “side” (as in “sidewall”),“higher”, “lower”, “over” and “under” are defined with respect to theconventional plane or surface being on the top surface of the wafer orsubstrate, regardless of the orientation of the wafer or substrate. Thefollowing detailed description is, therefore, not to be taken in alimiting sense, and the scope of the present invention is defined onlyby the appended claims, along with the full scope of equivalents towhich such claims are entitled.

A gate dielectric in a transistor has both a physical gate dielectricthickness and an equivalent oxide thickness (t_(eq)). The equivalentoxide thickness quantifies the electrical properties, such ascapacitance, of the gate dielectric in terms of a representativephysical thickness. t_(eq) is defined as the thickness of a theoreticalSiO₂ layer that would be required to have the same capacitance densityas a given dielectric, ignoring leakage current and reliabilityconsiderations.

A SiO₂ layer of thickness, t, deposited on a Si surface as a gatedielectric will have a t_(eq) larger than its thickness, t. This t_(eq)results from the capacitance in the surface channel on which the SiO₂ isdeposited due to the formation of a depletion/inversion region. Thisdepletion/inversion region can result in t_(eq) being from 3 to 6Angstroms (Å) larger than the SiO₂ thickness, t. Thus, with thesemiconductor industry driving to scale the gate dielectric equivalentoxide thickness to under 10 Å, the physical thickness requirement for aSiO₂ layer used for a gate dielectric would need to be approximately 4to 7 Å.

Additional requirements for a SiO₂ layer would depend on the gateelectrode used in conjunction with the SiO₂ gate dielectric. Using aconventional polysilicon gate would result in an additional undesirableincrease in t_(eq) for the SiO₂ layer. This additional thickness couldbe eliminated by using a metal gate electrode, though metal gates arenot currently used in typical complementary metal-oxide-semiconductorfield effect transistor (CMOS) technology. Thus, future devices would bedesigned towards a physical SiO₂ gate dielectric layer of about 4 Å orless.

Silicon dioxide is used as a gate dielectric, in part, due to itselectrical isolation properties in a SiO₂—Si based structure. Thiselectrical isolation is due to the relatively large band gap of SiO₂(8.9 eV), which makes it a good insulator. Significant reductions in itsband gap would eliminate it as a material for use as a gate dielectric.However, as the thickness of a SiO₂ layer decreases, the number ofatomic layers, or monolayers of the material in the thickness decreases.At a certain thickness, the number of monolayers will be sufficientlysmall that the SiO₂ layer will not have a complete arrangement of atomsas found in a thicker, or bulk layer. As a result of incompleteformation relative to a bulk structure, a thin SiO₂ layer of only one ortwo monolayers will not form a full band gap. The lack of a full bandgap in a SiO₂ gate dielectric may cause an effective short between anunderlying conductive silicon channel and an overlying polysilicon gate.This undesirable property sets a limit on the physical thickness towhich a SiO₂ layer can be scaled. The minimum thickness due to thismonolayer effect is thought to be about 7-8 Å. Therefore, for futuredevices to have a t_(eq) less than about 10 Å, other dielectrics thanSiO₂ need to be considered for use as a gate dielectric.

For a typical dielectric layer used as a gate dielectric, thecapacitance is determined as one for a parallel plate capacitance:C=k∈₀A/t, where k is the dielectric constant, ∈₀ is the permittivity offree space, A is the area of the capacitor, and t is the thickness ofthe dielectric. The thickness, t, of a material is related to its t_(eq)for a given capacitance, with SiO₂ having a dielectric constantk_(ox)=3.9, as

t=(k/k _(ox))t _(eq)=(k/3.9)t _(eq).

Thus, materials with a dielectric constant greater than that of SiO₂will have a physical thickness that can be considerably larger than adesired t_(eq), while providing the desired equivalent oxide thickness.For example, an alternate dielectric material with a dielectric constantof 10 could have a thickness of about 25.6 Å to provide a t_(eq) of 10Å, not including any depletion/inversion layer effects. Thus, a reducedequivalent oxide thickness for transistors can be realized by usingdielectric materials with higher dielectric constants than SiO₂.

The thinner equivalent oxide thickness required for lower transistoroperating voltages and smaller transistor dimensions may be realized bya significant number of materials, but additional fabricatingrequirements makes determining a suitable replacement for SiO₂difficult. The current view for the future of the microelectronicsindustry still predicts silicon-based devices. This requires that thegate dielectric employed be grown on a silicon substrate or siliconlayer, which places significant constraints on the substitute dielectricmaterial. During the formation of the dielectric on the silicon layer,there exists the possibility that a small layer of SiO₂ could be formedin addition to the desired dielectric. The result would effectively be adielectric layer consisting of two sub-layers in parallel with eachother and the silicon layer on which the dielectric is formed. Theresulting capacitance would be that of two dielectrics in series, andthe t_(eq) of the dielectric layer would be the sum of the SiO₂thickness and a multiplicative factor of the thickness, t, of thedielectric being formed, written as

t _(eq) =t _(SiO2)+(k _(ox) /k)t.

Thus, if a SiO₂ layer is formed in the process, the t_(eq) is againlimited by a SiO₂ layer. In the event that a barrier layer is formedbetween the silicon layer and the desired dielectric in which thebarrier layer prevents the formation of a SiO₂ layer, the t_(eq) wouldbe limited by the layer with the lowest dielectric constant. However,whether a single dielectric layer with a high dielectric constant or abarrier layer with a higher dielectric constant than SiO₂ is employed,the layer directly in contact, or interfacing with the silicon layermust provide a high quality interface to maintain high channel carriermobility. Preventing formation of an undesired SiO₂ layer is oneadvantage of using lower temperatures in atomic layer deposition (ALD).

One of the advantages of using SiO₂ as a gate dielectric has been thatthe formation of the SiO₂ layer results in an amorphous gate dielectric.Having an amorphous structure for a gate dielectric provides reducedleakage current problems associated with grain boundaries inpolycrystalline gate dielectrics, which may cause high leakage paths.Additionally, grain size and orientation changes throughout apolycrystalline gate dielectric layer may cause variations in the film'sdielectric constant, along with uniformity and surface topographyproblems. Typically, materials having the advantage of a high dielectricconstant relative to SiO₂ also have the disadvantage of a crystallineform, at least in a bulk configuration. The best candidates forreplacing SiO₂ as a gate dielectric are those with high dielectricconstant, which can be fabricated as a thin layer with an amorphousform. The increased amorphous nature of the film or layer is anotheradvantage of using lower temperatures in the ALD deposition process.

Candidates to replace SiO₂ include high-k dielectric materials. High-kmaterials include materials having a dielectric constant greater thansilicon dioxide, for example, dielectric materials having a dielectricconstant greater than about twice the dielectric constant of silicondioxide. An appropriate high-k gate dielectric should have a largeenergy gap (E_(g)) and large energy barrier heights with the siliconsubstrate for both electrons and holes. Generally, the band gap isinversely related to the dielectric constant for a high-k material,which lessens some advantages of the high-k material. A set of high-kdielectric candidates for replacing silicon oxide as the dielectricmaterial in electronic components in integrated circuits includes thelanthanide oxides such as Pr₂O₃, La₂O₃, Nd₂O₃, Sm₂O₃, Gd₂O₃, Dy₂O₃,Ce₂O₃, Tb₂O₃, Er₂O₃, EU₂O₃, LU₂O₃, Tm₂O₃, Ho₂O₃, Pm₂O₃, and Yb₂O₃. Othercandidates include various lanthanide silicates, zirconium oxide ZrO₂,titanium oxides such as TiO₂, and combinations of these materials. Suchhigh dielectric constant layers provide a significantly thinnerequivalent oxide thickness compared with a silicon oxide layer havingthe same physical thickness. Alternately, such dielectric layers providea significantly thicker physical thickness than a silicon oxide layerhaving the same equivalent oxide thickness. This increased physicalthickness aids in reducing leakage current.

Another consideration for selecting the material and method for forminga dielectric layer or film concerns the roughness of a dielectric on asubstrate. Surface roughness of the dielectric has a significant effecton the electrical properties of the gate oxide, and the resultingoperating characteristics of the transistor. The leakage current througha physical 1.0 nm gate dielectric may increase by a factor of 10 forevery 0.1 increase in the root-mean-square (RMS) roughness of thedielectric layer. The crystallization of an amorphous dielectric maycause the surface to become rough, and is another advantage of using ALDprecursors that allow a lower deposition temperature.

During a conventional sputtering deposition process, particles of thematerial to be deposited bombard the surface at a high energy. When aparticle hits the surface, some particles adhere, and other particlescause damage. High energy impacts remove body region particles, creatingpits. The surface of such a deposited layer may have a rough contour dueto the rough interface at the body region.

In an embodiment, a dielectric having a substantially smooth surfacerelative to other processing techniques is formed using atomic layerdeposition (ALD). Further, forming such a dielectric layer or film usingatomic layer deposition can provide for controlling transitions betweenmaterial layers. As a result of such control, atomic layer depositeddielectrics may have an engineered transition with a substrate surface,or may be formed with many thin layers of different dielectric materialsto enable selection of the dielectric constant to a value between thatavailable from pure dielectric compounds.

ALD, which may also be known as atomic layer epitaxy (ALE), is amodification of chemical vapor deposition (CVD) and may also be called“alternatively pulsed-CVD.” In ALD, gaseous precursors are introducedone at a time to the substrate surface mounted within a reaction chamber(or reactor). This introduction of the gaseous precursors takes the formof sequential pulses of each gaseous precursor. In a pulse of aprecursor gas, the precursor gas is made to flow into a specific area orregion for a short period of time. Between the pulses, the reactionchamber is purged with a gas, which in many cases is an inert gas,and/or evacuated.

In the first reaction step of the ALD process the first precursorsaturates and is chemisorbed at the substrate surface, during the firstpulsing phase. Subsequent pulsing with a purging gas removes excessprecursor from the reaction chamber, specifically the precursor that hasnot been chemisorbed.

The second pulsing phase introduces a second precursor to the substratewhere the growth reaction of the desired layer takes place, with areaction thickness that depends upon the amount of the chemisorbed firstprecursor. Subsequent to the film growth reaction, reaction byproductsand precursor excess are purged from the reaction chamber. With aprecursor chemistry where the precursors adsorb and aggressively reactwith each other on the substrate, one ALD cycle can be performed in lessthan one second in properly designed flow type reaction chambers.Typically, precursor pulse times range from about 0.5 sec to about 2 to3 seconds.

In ALD processes, the saturation of all the reaction and purging phasesmakes the film growth self-limiting. This self-limiting growth resultsin large area uniformity and conformality, which has importantapplications for such cases as planar substrates, deep trenches, and inthe processing of porous silicon and high surface area silica andalumina powders. Significantly, ALD provides for controlling film orlayer thickness in a straightforward manner by controlling the number ofgrowth cycles.

ALD was originally developed to manufacture luminescent and dielectricfilms needed in electroluminescent displays. ALD has been studied forthe growth of different epitaxial II-V and II-VI films, nonepitaxialcrystalline or amorphous oxide and nitride films, and multilayerstructures of these. There also has been considerable interest towardsthe ALD growth of silicon and germanium, but due to the difficultprecursor chemistry, this has not been very successful.

The precursors used in an ALD process may be gaseous, liquid or solid.However, liquid or solid precursors should be volatile with high vaporpressures or low sublimation temperatures. The vapor pressure should behigh enough for effective mass transportation. In addition, solid andsome liquid precursors may need to be heated inside the reaction chamberand introduced through heated tubes to the substrates. The necessaryvapor pressure should be reached at a temperature below the substratetemperature to avoid the condensation of the precursors on thesubstrate. Due to the self-limiting growth mechanisms of ALD, relativelylow vapor pressure solid precursors may be used, though evaporationrates may vary somewhat during the process because of changes in surfacearea.

Other desirable characteristics for ALD precursors include thermalstability at the substrate temperature, since decomposition may destroysurface control and accordingly the advantages of the ALD method, whichrelies on the reaction of the precursor at the substrate surface. Aslight decomposition, if slow compared to the ALD growth, can betolerated. The precursors should chemisorb on, or react with thesurface, though the interaction between the precursor and the surface aswell as the mechanism for the adsorption is different for differentprecursors. The molecules at the substrate surface should reactaggressively with the second precursor, which may be called a reactant,to form the desired film. Additionally, precursors should not react withthe film to cause etching, and precursors should not dissolve in thefilm. The use of highly reactive precursors in ALD may contrast with theprecursors for conventional metallo-organic CVD (MOCVD) type reactions.Further, the by-products of the reaction should be gaseous in order toallow their easy removal from the reaction chamber during a purge stage.Finally, the by-products should not react or adsorb on the surface.

In a reaction sequence ALD (RS-ALD) process, the self-limiting processsequence involves sequential surface chemical reactions. RS-ALD relieson chemistry between a reactive surface and a reactive molecularprecursor. In an RS-ALD process, molecular precursors are pulsed intothe ALD reaction chamber separately. The metal precursor reaction at thesubstrate is typically followed by an inert gas pulse (or purge) toremove excess precursor and by-products from the reaction chamber priorto an input pulse of the next precursor of the fabrication sequence.

By the use of RS-ALD processes, films can be layered in equal meteredsequences that are all identical in chemical kinetics, deposition percycle, composition, and thickness. RS-ALD sequences generally depositless than a full layer per cycle. Typically, a deposition or growth rateof about 0.25 to about 2.00 Å per RS-ALD cycle can be realized.

The advantages of ALD include continuity at an interface and avoidingpoorly defined nucleating regions, which are typical for thin chemicalvapor deposition (<20 Å) and physical vapor deposition (<50 Å),conformality over a variety of substrate topologies due to itslayer-by-layer deposition technique, use of low temperature and mildlyoxidizing processes, lack of dependence on the reaction chamber, growththickness dependent solely on the number of cycles performed, andability to engineer multilayer laminate films with resolution of one totwo monolayers. ALD processes allow for deposition control on the orderof single monolayers and the ability to deposit monolayers of amorphousfilms.

A cycle of an ALD deposition sequence includes pulsing a precursormaterial, pulsing a purging gas for the precursor, pulsing a reactantprecursor, and pulsing the reactant's purging gas, resulting in a veryconsistent deposition thickness that depends upon the amount of thefirst precursor that adsorbs onto, and saturates, the surface. Thiscycle may be repeated until the desired thickness is achieved in asingle material dielectric layer, or may be alternated with pulsing athird precursor material, pulsing a purging gas for the third precursor,pulsing a fourth reactant precursor, and pulsing the reactant's purginggas. There need not be a reactant gas if the precursor can interact withthe substrate directly, as in the case of a dopant metal layer on adielectric layer, as claimed in the present subject matter. In the casewhere the thickness of the first series of cycles results in adielectric layer that is only a few molecular layers thick, and thesecond series of cycles also results in a different dielectric layerthat is only a few molecular layers thick, this may be known as ananolayer material or a nanolaminate. A nanolaminate means a compositefilm of ultra-thin layers of two or more different materials in alayered stack, where the layers are alternating layers of differentmaterials having a thickness on the order of a nanometer, and may be acontinuous film only a single monolayer thick of the material. Thenanolayers are not limited to alternating single layers of eachmaterial, but may include having several layers of one materialalternating with a single layer of the other material, to obtain adesired ratio of the two or more materials. Such an arrangement mayobtain a dielectric constant that is between the values of the two ormore materials singly. A nanolaminate may also include having severallayers of one material formed by an ALD reaction either over or under asingle layer of a different material formed by another type of reaction,such as a MOCVD reaction. The layers of different materials may remainseparate after deposition, or they may react with each other to form analloy layer. The alloy layer may be viewed as a doping layer, and theproperties of the dielectric layer may be varied by such doping. Thepresent subject matter uses the substitutional incorporation of cationsof specific group IIA elements having certain sizes to reduce theleakage currents found in amorphous titanium oxide layers. The resultare amorphous doped titanium oxide layers having a formula ofa-Ti_(1-y)L_(y)O_(x), where y ranges from 0.1 to 0.3, and L representsone of the lanthanide materials including samarium, europium,gadolinium, holmium, erbium and thulium. Other lanthanide materials suchas dysprosium and neodymium, and other early transition metals such aszirconium having higher valence levels may also be helpful, especiallyin combinations.

In an embodiment, a layer of titanium oxide is formed on a substratemounted in a reaction chamber using sequential atomic layer deposition,which may also be known as RS-ALD. An embodiment includes forming thetitanium oxide layers using a precursor gas such as titaniumtetra-chloride, having a chemical formula of TiCl₄, and water vapor. Anembodiment includes forming the lanthanide or lanthanide oxide layerusing a diketonate chelate precursor gas such as tetramethylheptanedione or dipivaloylmethane, and ozone. Other solid or liquidprecursors may be used in an appropriately designed reaction chamber.The use of such precursors in an ALD reaction chamber may result inlower deposition temperatures in the range of 100° C. to 250° C. Purgegases may include nitrogen, helium, argon or neon. The lanthanide dopedtitanium films formed may have good thermal and electrical properties,with a high dielectric constant k=50 to 100. Such films may survive hightemperature anneals (sometimes used to reduce fixed surface statecharges and improve metal to semiconductor resistance) of up to 1000°C., and have low leakage currents of less than 2×10⁻⁷ A/cm² at electricfield strengths of one MVolt/cm.

FIG. 1 shows an embodiment of an atomic layer deposition system 100 forforming a dielectric film. The elements depicted permit discussion ofthe present invention such that those skilled in the art may practicethe present invention without undue experimentation. In FIG. 1, asubstrate 108 on a heating element/wafer holder 106 is located inside areaction chamber 102 of ALD system 100. The heating element 106 isthermally coupled to substrate 108 to control the substrate temperature.A gas-distribution fixture 110 introduces precursor, reactant and purgegases to the substrate 108 in a uniform fashion. The gases introduced bythe gas distribution fixture, sometimes referred to a showerhead, reactwith the substrate 108, and any excess gas and reaction products areremoved from chamber 102 by vacuum pump 104 through a control valve 105.Each gas originates from individual gas sources 114, 118, 122, 126, 130,and 134, with a flow rate and time controlled by mass-flow controllers116, 120, 124, 128, 132 and 136, respectively. Gas sources 122 and 130provide a precursor gas, either by storing the precursor as a gas or byproviding for evaporating a solid or liquid material to form theselected precursor gas.

Also included in the system are purging gas sources 114 and 118, coupledto mass-flow controllers 116 and 120, respectively. The embodiment mayuse only one of the purge gases for all four disclosed illustrativepurging steps, or both purge gases may be used simultaneously, oralternately as required for the particular desired result. Furthermore,additional purging gas sources can be constructed in ALD system 100, onepurging gas source for each different precursor and reactant gas, forexample. For a process that uses the same purging gas for multipleprecursor gases, fewer purging gas sources may be required for ALDsystem 100. The precursor, reactant and purge gas sources are coupled bytheir associated mass-flow controllers to a common gas line or conduit112, which is coupled to the gas-distribution fixture 110 inside thereaction chamber 102. Gas conduit 112 may also be coupled to anothervacuum pump, or exhaust pump, not shown, to remove excess precursorgases, purging gases, and by-product gases at the end of a purgingsequence from the gas conduit 112.

Vacuum pump, or exhaust pump, 104 is coupled to chamber 102 by controlvalve 105, which may be a mass-flow valve, to remove excess precursorgases, purging gases, and by-product gases from reaction chamber 102 atthe end of a purging sequence. For convenience, control displays,mounting apparatus, temperature sensing devices, substrate maneuveringapparatus, and necessary electrical connections as are known to thoseskilled in the art are not shown in FIG. 1. Though ALD system 100 iswell suited for practicing the present invention, other commerciallyavailable ALD systems may also be used.

The use, construction and operation of reaction chambers for depositionof films are understood by those of ordinary skill in the art ofsemiconductor fabrication. The present invention may be practiced on avariety of such reaction chambers without undue experimentation.Furthermore, one of ordinary skill in the art will comprehend thenecessary detection, measurement, and control techniques in the art ofsemiconductor fabrication upon reading the disclosure.

The elements of ALD system 100 may be controlled by a computer using acomputer readable medium having computer executable instructions tocontrol the individual elements such as pressure, temperature, and gasflow within ALD system 100. To focus on the use of ALD system 100 in thevarious embodiments of the present invention, the computer is not shown.

FIG. 2 illustrates a flow diagram of operational steps for an embodimentof a method to form a nanolaminate dielectric layer having anillustrative two different materials. At 202, a substrate is prepared toreact immediately with, and chemisorb the first precursor gas. Thispreparation will remove contaminants such as thin organic films, dirt,and native oxide from the surface of the substrate, and may include ahydrofluoric acid rinse, or a sputter etch in the reaction chamber 102.At 206 a first precursor material enters the reaction chamber for apredetermined length of time, for example 0.5-2.0 seconds. The firstprecursor material is chemically adsorbed onto the surface of thesubstrate, the amount depending upon the temperature of the substrate,in one embodiment 300° C. and the presence of sufficient flow of theprecursor material. In addition, the pulsing of the precursor may use apulsing period that provides uniform coverage of an adsorbed monolayeron the substrate surface, or may use a pulsing period that providespartial formation of a monolayer on the substrate surface. An exampleprecursor gas includes TiCl₄.

At 208 a first purge gas enters the reaction chamber for a predeterminedlength of time sufficient to remove substantially all of thenon-chemisorbed first precursor material. Typical times may be 1.0-2.0seconds with a purge gas comprising nitrogen, argon, neon, combinationsthereof, or other gases such as hydrogen. At 210 a first reactant gasenters the chamber for a predetermined length of time, sufficient toprovide enough of the reactant to chemically combine with the amount ofchemisorbed first precursor material on the surface of the substrate.Typical reactant materials include mildly oxidizing materials such aswater vapor, but may in general also include hydrogen peroxide, nitrogenoxides, ozone and oxygen gas, and combinations thereof. At 212 a secondpurge gas, which may be the same or different from the first purge gas,enters the chamber for a predetermined length of time, sufficient toremove substantially all non-reacted materials and any reactionbyproducts from the chamber.

At 214 a decision is made as to whether or not the thickness of thefirst dielectric material in the dielectric has reached the desiredthickness, or whether another deposition cycle is required. If anotherdeposition cycle is needed, then the operation returns to 206, until thedesired first dielectric layer is completed, at which time the processmoves on to the deposition of the second material at 215. At 215 asecond precursor material enters the reaction chamber for apredetermined length of time, typically 0.5-2.0 seconds. The secondprecursor material is chemically adsorbed onto the surface of thesubstrate, in this case the top surface of the first dielectricmaterial, the amount of absorption depending upon the temperature of thesubstrate, and the presence of sufficient flow of the precursormaterial. In addition, the pulsing of the precursor may use a pulsingperiod that provides uniform coverage of an adsorbed monolayer on thesubstrate surface, or may use a pulsing period that provides partialformation of a monolayer on the substrate surface.

At 216 the first purge gas is shown as entering the chamber, but theinvention is not so limited. The purge gas used in the second dielectricmaterial deposition may be the same or different from either of the twopreviously noted purge gases, and FIG. 1 could be shown as having morethan the two purge gases shown. The purge cycle continues for apredetermined length of time sufficient to remove substantially all ofthe non-chemisorbed second precursor material.

At 218 an illustrative second reactant gas, which may be the same ordifferent from the first reactant gas, enters the chamber for apredetermined length of time, sufficient to provide enough of thereactant to chemically combine with the amount of chemisorbed secondprecursor material on the surface of the substrate. In an embodiment,there is no second reactant gas, and the precursor chemically reactswith the first material to form an alloy or a doped layer of the firstmaterial. At 220 another purge gas enters the chamber, which may be thesame or different from any of the three previously discussed purgegases, for a predetermined length of time, sufficient to removesubstantially all non-reacted materials and any reaction byproducts fromthe chamber.

At 222 a decision is made as to whether or not the thickness of thesecond material in the nanolaminate dielectric has reached the desiredthickness, or whether another deposition cycle is required. If anotherdeposition cycle is needed, then the operation returns to 215, until thedesired second layer is completed. The desired thicknesses of the firstand second materials in the dielectric may not be the same thickness,and there may be more deposition cycles for one material as compared tothe other. If the second layer has reached the desired thickness, theprocess moves on to a decision at 224 of whether the number of layers ofthe first and second materials has reached the desired number. In thisillustrative embodiment a single layer of the first dielectric and asingle layer of the second material have been completed at this point inthe process. If more than a single layer of each material is desired,the process moves back to another deposition of the first dielectricmaterial at 206. After the number of interleaved layers of dielectricsone and two has reached the desired value, the deposition ends at 226.Because the dielectric values of the ALD oxides in the describedembodiment are high, for example lanthanide doped titanium oxide mayhave a dielectric constant of 50 to 100, and because the highlycontrolled layer thickness may be a single monolayer for each one of theinterleaved dielectric layers, the physical thickness needed to obtainthe equivalent dielectric properties of a very thin silicon dioxidelayer may have from two to ten layers of the two dielectric materialsdescribed in the embodiments.

The embodiments described herein provide a process for growing adielectric film having a wide range of useful equivalent oxidethickness, t_(eq), associated with a dielectric constant in the rangefrom about 50 to about 100. This range of dielectric constants providesfor a t_(eq) ranging up to 4% relative to a given silicon dioxidethickness, that is, it appears to be equivalent to a silicon dioxidelayer that is 25 times thinner, providing enhanced probability forreducing leakage current. Controlling the amount of lanthanide doping inthe titanium film to 10 to 30% results in relatively low leakage currentas compared to pure titanium oxides. Additionally, the novel process canbe implemented to form transistors, capacitors, memory devices, andother electronic systems including information handling devices. Theinvention is not limited to two dielectric materials, and the equipmentdescribed in FIG. 1 could have included a precursor and reactant 3, 4,which are not described for simplicity, or there may be two or moresimultaneous flows of different lanthanide precursors during the secondmaterial deposition.

FIG. 3 illustrates a single transistor 300 in an embodiment of a methodto form a dielectric layer containing an ALD deposited lanthanide dopedtitanium gate oxide layer. This embodiment may be implemented with thesystem 100 of FIG. 1 used as an atomic layer deposition system. Asubstrate 302 is prepared, typically a silicon or silicon containingmaterial. In other embodiments, germanium, gallium arsenide,silicon-on-sapphire substrates, or other suitable substrates may also beused. The preparation process includes cleaning substrate 302 andforming various layers and regions of the substrate, such as draindiffusion 304 and source diffusion 306 of an illustrative metal oxidesemiconductor (MOS) transistor 300, prior to forming a gate dielectric.In an embodiment, the substrate is cleaned to provide an initialsubstrate depleted of its native oxide. In an embodiment, the initialsubstrate is cleaned to provide a hydrogen-terminated surface. In anembodiment, a silicon substrate undergoes a final hydrofluoric (HF)rinse prior to ALD processing to provide the silicon substrate with ahydrogen-terminated surface without a native silicon oxide layer.Cleaning immediately preceding atomic layer deposition aids in reducingan occurrence of silicon oxide as an interface between the siliconsubstrate and the dielectric formed using the atomic layer depositionprocess. The sequencing of the formation of the regions of thetransistor being processed may follow the generally understoodfabrication of a MOS transistor as is well known to those skilled in theart.

The dielectric covering the area on the substrate 302 between the sourceand drain diffused regions 304 and 306 may be deposited by ALD in thisillustrative embodiment, and may comprise one or more titanium oxidelayers 310 and 314, each potentially formed of many individual layers.There is shown a sequentially interleaved lanthanide or lanthanide oxidelayer 312. Alternatively, there may be other combinations of interleavedand non-interleaved layers of varying thickness and deposition method.This nanolaminate dielectric layer is referred to as the gate oxide, andwhile shown as distinct layers for clarity, is a single alloyed layer,or doped layer. There may be a diffusion barrier layer inserted betweenthe first dielectric layer 310 and the substrate 302 to prevent metalcontamination from affecting the electrical properties of the device.The illustrative embodiment shows the two titanium dielectric layers 310and 314 having the same thickness, however the desired dielectricproperties of the nanolaminate film may be best achieved by adjustingthe ratio of the thickness of the two dielectric layers to differentvalues. The transistor 300 has a conductive material forming a gate 318in this illustrative embodiment, but the nanolaminate dielectric mayalso be used in a floating gate device such as an EEPROM transistor, aseither one or both of the floating gate and the control gate oxidelayers. The conductive material may be polysilicon or various metals.

In an illustrative embodiment, gate dielectric (layers 310-314) includea tunnel gate insulator and a floating gate dielectric in a flash memorydevice. Use of dielectric layers containing a nanolaminate atomic layerdeposited dielectric layer for a gate dielectric and/or floating gatedielectric in which the dielectric layer contacts a conductive layer isnot limited to silicon based substrates, but may be used with a varietyof semiconductor substrates.

Embodiments of methods for forming dielectric layers containing an ALDdeposited dielectric layer contacting a conductive layer may also beapplied to forming capacitors in various integrated circuits, memorydevices, and electronic systems. In an embodiment including a capacitor400 illustrated in FIG. 4, a method includes forming a first conductivelayer 402, a second conductive layer 404, having a nanolaminatedielectric having interleaved layers 406-414 of two different materials,formed between the two conductive layers. The conductive layers 402 and404 may include metals, doped polysilicon, silicided metals, polycides,or conductive organic compounds, without affecting the teachings of thisembodiment. The sequencing and thickness of the individual layersdepends on the application and may include a single layer of eachmaterial, one layer of one of the materials and multiple layers of theother, or other combinations of layers including different layerthicknesses. By selecting each thickness and the composition of eachlayer, a nanolaminate structure can be engineered to have apredetermined dielectric constant and composition. In an embodiment thetotal of layers 406 and 414 are ten times the thickness of layer 410,providing a 10% doping of layer 410 material (for example a lanthanideoxide) in the layer 406/414 material (for example titanium oxide).Although the oxide layers are shown in this illustrative example asbeing distinct layers, the oxide may be alloyed together to form asingle material layer. Structures such as the nanolaminate structureshown in FIGS. 3 and 4 may be used in NROM flash memory devices as wellas other integrated circuits. Transistors, capacitors, and other deviceshaving dielectric films may be implemented into memory devices andelectronic systems including information handling devices. Embodimentsof these information handling devices include wireless systems,telecommunication systems, computers and integrated circuits.

FIG. 5 illustrates a diagram for an electronic system 500 having one ormore devices having a dielectric layer containing an atomic layerdeposited oxide layer formed according to various embodiments of thepresent invention. Electronic system 500 includes a controller 502, abus 504, and an electronic device 506, where bus 504 provides electricalconductivity between controller 502 and electronic device 506. Invarious embodiments, controller 502 and/or electronic device 506 includean embodiment for a dielectric layer containing sequentially depositedALD layers as previously discussed herein. Electronic system 500 mayinclude, but is not limited to, information handling devices, wirelesssystems, telecommunication systems, fiber optic systems, electro-opticsystems, and computers.

FIG. 6 depicts a diagram of an embodiment of a system 600 having acontroller 602 and a memory 606. Controller 602 and/or memory 606includes a dielectric layer having a nanolaminate RS-ALD dielectriclayer. System 600 also includes an electronic apparatus 608, and a bus604, where bus 604 may provide electrical conductivity and datatransmission between controller 602 and electronic apparatus 608, andbetween controller 602 and memory 606. Bus 604 may include an address, adata bus, and a control bus, each independently configured. Bus 604 alsouses common conductive lines for providing address, data, and/orcontrol, the use of which may be regulated by controller 602. In anembodiment, electronic apparatus 608 includes additional memory devicesconfigured similarly to memory 606. An embodiment includes an additionalperipheral device or devices 610 coupled to bus 604. In an embodimentcontroller 602 is a processor. Any of controller 602, memory 606, bus604, electronic apparatus 608, and peripheral device or devices 610 mayinclude a dielectric layer having an ALD deposited oxide layer inaccordance with the disclosed embodiments.

System 600 may include, but is not limited to, information handlingdevices, telecommunication systems, and computers. Peripheral devices610 may include displays, additional storage memory, or other controldevices that may operate in conjunction with controller 602 and/ormemory 606. It will be understood that embodiments are equallyapplicable to any size and type of memory circuit and are not intendedto be limited to a particular type of memory device. Memory typesinclude a DRAM, SRAM (Static Random Access Memory) or Flash memories.Additionally, the DRAM could be a synchronous DRAM commonly referred toas SGRAM (Synchronous Graphics Random Access Memory), SDRAM (SynchronousDynamic Random Access Memory), SDRAM II, and DDR SDRAM (Double Data RateSDRAM), as well as other emerging DRAM technologies.

Formation of nanolaminate lanthanide doped titanium oxide layers by anALD deposition may be realized using a diketonate type chelate precursorchemical, such as L(thd)₃, and an oxidizing precursor, such as ozone.Further, such doped dielectric films formed in relatively lowtemperatures, such as 250° C. or lower, may be amorphous and possesssmooth surfaces. Such oxide films may provide enhanced electricalproperties as compared to physical deposition methods, such assputtering, or typical chemical layer depositions, due to their smoothersurface, and reduced damage, resulting in reduced leakage current.Additionally, such dielectric layers provide a significantly thickerphysical thickness than a silicon oxide layer having the same equivalentoxide thickness, where the increased thickness may also reduce leakagecurrent issues. These properties of RS-ALD deposited dielectric layersallow for application as dielectric layers in electronic devices andsystems.

Capacitors, transistors, higher level ICs or devices including memorydevices, and electronic systems are constructed utilizing the novelprocess for forming a dielectric film having an ultra thin equivalentoxide thickness, t_(eq). Gate dielectric layers or films containingatomic layer deposited lanthanide oxide are formed having a dielectricconstant (k) substantially higher than that of silicon oxide, such thatthese dielectric films possess an equivalent thickness, t_(eq), thinnerthan SiO₂ gate dielectrics of the same physical thickness.Alternatively, the high dielectric constant relative to silicon dioxideallows the use of much larger physical thickness of these high-kdielectric materials for the same t_(eq) of SiO₂. Film having therelatively larger physical thickness aids in processing gate dielectricsand other dielectric layers in electronic devices and systems, andimproves the electrical properties of the dielectrics.

CONCLUSION

Embodiments for a method for forming an electronic device includeforming a dielectric layer by using an atomic layer deposition (ALD)technique to form a dielectric having a lanthanide, or a lanthanideoxide (for example Sm₂O₃) doped titanium oxide (TiOx) layer. Titanium iselemental metal number 22, and the lanthanide series includes elementnumbers 57 to element 71. Titanium oxide films, for example TiO₂titanium dioxide, may be atomic layer deposited using various precursorssuch as titanium tetrachloride TiCl₄ and water vapor H₂O at atemperature of between 100 to 250° C. Lanthanide or lanthanide oxidefilms may be atomic layer deposited using various other precursors, suchas a volatile diketonate chelates, for example2,2,6,6-tetramethyl-3,5-heptanedione, and ozone at less than 250° C.

These disclosed layers may have a very tightly controlled thickness foreach deposition cycle that depends on the chemical saturation of thesubstrate surface. The surface of the layer formed by ALD may also bevery smooth and continuous, even over sharp underlying topography. Thedeposition cycles may also be alternated between the two differentmaterials, and the resulting layer may be either a nanolaminate of thetwo or more different oxides, or the oxides may form an alloy with eachother if the similarity between the two metals results in misciblematerials. In either case the film properties may vary depending uponthe ratio of the two or more different materials, and thus materials maybe formed that have engineered properties.

The low temperature deposition of ALD depositions may result indielectric layers that are amorphous even after subsequent heat cyclessuch as densification and mild oxidative repair cycles. Silicon dioxidelayers grown by oxidation of silicon substrates are amorphous, and thesubsequent heat cycles typically used in semiconductor fabrication donot substantially change the amorphous nature of the silicon dioxide.This may be important since crystallization of a dielectric may causethe surface to become rough, which may cause greatly increased leakageacross the dielectric. The crystallization of a dielectric may alsocause the covering conductive layer to form sharp spikes, which mayincrease the local electric field to a level that may cause dielectricbreakdown and result in a short circuit.

The dielectric structure is formed by depositing titanium by atomiclayer deposition (ALD) onto a substrate surface using precursorchemicals to form a layer of TiO₂ or some other titanium oxide, followedby ALD depositing of one or more lanthanide or lanthanide oxidematerials selected from samarium, europium, gadolinium, holmium, erbiumand thulium, onto the substrate using precursor chemicals and repeatingas often as necessary to form a dielectric structure of the requiredthickness and atomic percentage of lanthanide doping. An embodiment mayhave a lanthanide percentage of from 10 to 30%. An alloyed amorphousdielectric layer of lanthanide doped titanium oxide may be beneficiallyused because the high dielectric constant (high-k) of from about 50-110of the film, as compared to 3.9 for silicon dioxide, and the excellentcurrent leakage value, provides the functionality of a much thinnersilicon dioxide film without the reliability loss consequent to usingsuch physically thin films.

An embodiment may include a method of forming an amorphous dielectriclayer on a substrate by atomic layer deposition at a predeterminedtemperature, the dielectric layer containing at least one titanium oxidelayer doped by at least one layer of a lanthanide selected from the listincluding samarium, europium, gadolinium, holmium, erbium and thulium.The dielectric layer may then be annealed at least once in either a nonoxidizing ambient to make the layer more dense, or in a mildly oxidizingambient to repair defects in the dielectric layer, or both. Anelectrically conductive layer may then be formed on the dielectriclayer. The predetermined temperature may be in a range of approximately100° C. to 250° C.

The disclosed methods may be used to form transistors, capacitors, andnon volatile memory devices. The amorphous dielectric layer may be anumber of individual titanium oxide layers, with at least one lanthanidelayer interleaved between each one of the titanium oxide layers. Thetitanium oxide layers may be a group of continuous mono-layers oftitanium oxide, each approximately 0.12 nm in thickness. The atomicratio of the lanthanide to the titanium may be from 10 to 30%, and maybe a single lanthanide or a mixture of two or more lanthanides to obtaina dielectric constant value in the range from 50 to 100. The properchoice of titanium to lanthanide ratio may be selected to obtain aleakage current of less than 10⁻⁸ A/cm², and a breakdown voltage ofgreater than 2.0 MV/cm. The dielectric layer may be very smooth, havinga root mean square surface roughness that is less than one tenth of thelayer thickness, which may improve the breakdown voltage and leakagecurrent.

The lanthanide layer may be formed of two different lanthanidessequentially deposited between the titanium oxide layers, or the twolanthanides may be deposited simultaneously. The dielectric may beannealed in an inert ambient at a temperature less than 1000° C. forabout one minute, and then annealed in a mildly oxidizing ambient at atemperature of less than 700° C. for about one minute, and the oxidizingambient may be at a reduced pressure of about 1 Torr of either oxygen,ozone, nitrous oxide, hydrogen peroxide and water vapor, or combinationsthereof in order to improved the dielectric properties.

The atomic layer deposition may have an activated substrate surface at apreselected temperature exposed to a titanium-containing first precursormaterial for a first time period and flow volume, which saturates thesubstrate surface. Then a first purge for a second time period removessubstantially all of the non-adsorbed portion of the first precursormaterial from the substrate surface. Then the substrate surface isexposed to a first oxidizing reactant material which reacts with theadsorbed first precursor material on the substrate surface to form afirst titanium oxide material to complete a first deposition cycle. Thedeposition cycle is repeated until a desired first dielectric materialthickness is obtained. Then the substrate surface is exposed to alanthanide-containing second precursor material to saturate thesubstrate surface with the second precursor material, which is repeatedto obtain the second material thickness. Alternatively, the lanthanidedopant may be in the form of a lanthanide oxide layer formed in thesecond deposition cycle by adding a second oxidizing reactant material.

In one embodiment, the first precursor may be titanium tetrachloride(TiCl₄) and the reactant may be water vapor (H₂O). The depositiontemperature is less than 250° C. The second precursor material may havea formula L(thd)₃, where L is one of the lanthanide materials, and thdis 2,2,6,6-tetramethyl-3,5-heptanedione. The lanthanide doped titaniumoxide film may be a continuous layer having a root mean square surfaceroughness of less than 10 angstroms and a current leakage rate of lessthan 2×10⁻⁷ amps per cm at an electric field strength of 1 megavolt percm. The amorphous dielectric layer may have an equivalent oxidethickness of less than 10 Angstroms, or less than 7 Angstroms, or evenless than 4 Angstroms, and a breakdown voltage of greater than 2.5 MV/cmdue to the higher physical thickness, the smoothness of the amorphousdielectric, and the proper atomic percentage of lanthanide dopant in thetitanium oxide film.

Embodiments may generally include structures used for capacitors,transistors, memory devices, and electronic systems with dielectriclayers containing an atomic layer deposited lanthanide doped titaniumoxide dielectric, and methods for forming such structures.

Although specific embodiments have been illustrated and describedherein, it will be appreciated by those of ordinary skill in the artthat any arrangement that is calculated to achieve the same purpose maybe substituted for the specific embodiments shown. This application isintended to cover any adaptations or variations of embodiments of thepresent invention. It is to be understood that the above description isintended to be illustrative, and not restrictive, and that thephraseology or terminology employed herein is for the purpose ofdescription and not of limitation. Combinations of the above embodimentsand other embodiments will be apparent to those of skill in the art uponstudying the above description. The scope of the present inventionincludes any other applications in which embodiments of the abovestructures and fabrication methods are used. The scope of theembodiments of the present invention should be determined with referenceto the appended claims, along with the full scope of equivalents towhich such claims are entitled.

1. A capacitor, comprising: a first conductive layer; an amorphous dielectric layer disposed on the first conductive layer comprising a titanium oxide film doped with from 10 to 30 atomic percent of a lanthanide material selected from the list including samarium, europium, gadolinium, holmium, erbium and thulium having a dielectric constant of from 50 to 100; and a second conductive layer disposed on the dielectric layer.
 2. The capacitor of claim 1, wherein the amorphous dielectric layer has a root mean square surface roughness of less than 10 angstroms and a current leakage rate of less than 2×10⁻⁷ amps per cm² at an electric field strength of 1 megavolt per cm.
 3. The capacitor of claim 1, wherein the amorphous dielectric layer has an equivalent oxide thickness of less than 10 Angstroms, and a breakdown voltage of greater than 2.5 MV/cm.
 4. An electronic device comprising: a dielectric layer containing an atomic layer deposited dielectric layer of lanthanide doped titanium oxide in an integrated circuit; and a conductive layer contacting the dielectric layer.
 5. The electronic device of claim 4 wherein the lanthanide doped titanium oxide layer comprises an amorphous layer.
 6. The electronic device of claim 4 wherein the lanthanide doped titanium oxide layer comprises at least two layers of titanium oxide and at least one layer of a lanthanide oxide selected from the list comprising at least one of samarium, europium, gadolinium, holmium, erbium and thulium oxide disposed between the at least two layers of titanium oxide in an integrated circuit
 7. The electronic device of claim 4, wherein the electronic device includes a memory having the dielectric as a gate insulator in a transistor device, where the dielectric comprises a lanthanide oxide having at least 10% composition of the atomic percent of the dielectric film, and a dielectric constant is about
 100. 8. An electronic system comprising: a controller; an electronic device coupled to the controller, wherein the electronic device includes: a dielectric layer comprising a lanthanide doped titanium oxide in an integrated circuit and a dielectric constant of from 50 to 100; and a conductive layer contacting the dielectric layer.
 9. The electronic system of claim 8, wherein the dielectric layer comprises an amorphous dielectric material including a lanthanide material selected from the list including samarium, europium, gadolinium, holmium, erbium and thulium, having an atomic percent of from 10 to 30% by weight of the dielectric film.
 10. The electronic system of claim 8, wherein the dielectric layer includes at least one amorphous material having a vertical thickness of a single molecular layer formed by atomic layer deposition of titanium oxide, at least one amorphous material having a vertical thickness of a single molecular layer formed by atomic layer deposition of a lanthanide oxide, and at least one amorphous material having a vertical thickness of a single molecular layer formed by atomic layer deposition of titanium oxide.
 11. A transistor, comprising: a semiconductor substrate; a dielectric layer disposed on the semiconductor layer having a vertical thickness of less than 100 Angstroms, a dielectric constant of greater than 30, and a breakdown voltage of greater than 2.5 MV/cm; and a conductive layer disposed on the dielectric layer.
 12. The transistor of claim 11, wherein the dielectric layer includes an amorphous nature and includes at least two layers of an dielectric material having at least one metal from column IVA of the periodic table, and at least one layer of a dielectric material having at least one lanthanide material disposed between the at least two layers, the dielectric layer having a silicon dioxide equivalent thickness of less than 10 Angstroms.
 13. The transistor of claim 12, wherein the dielectric layer comprises at least one of a titanium oxide film and a zirconium oxide film doped with 0.1 to 30 atomic percent of a material selected from the list including samarium, europium, gadolinium, holmium, erbium, thulium, dysprosium and neodymium.
 14. The transistor of claim 13, wherein the dielectric layer has a root mean square surface roughness of less than 10 Angstroms and a current leakage rate of 1.0×10⁻⁸ to 2×10⁻⁷ amps per cm at an electric field strength of 1.0 to 2.0 megavolt per cm.
 15. The transistor of claim 14, wherein the dielectric layer comprises a first plurality of layers comprising titanium oxide and a second plurality of layers comprising a lanthanide oxide interleaved between selected ones of the first plurality of layers to form a nano-laminated dielectric layer.
 16. The transistor of claim 15, wherein one of the first plurality of layers directly contacts the semiconductor substrate.
 17. The transistor of claim 16, wherein the first plurality of layers each have a thickness of 0.12 nm n.
 18. An electronic device comprising: a dielectric layer containing a first plurality of atomic layer deposited dielectric layers of titanium dioxide having an approximately formula of TiO₂, interleaved with a second plurality of atomic layer deposited dielectric layers of lanthanide oxide having an approximately formula of LaO₂; and a conductive layer contacting the dielectric layer.
 19. The electronic device of claim 18, wherein the second plurality comprises 10% of an atomic percent of the first plurality, the dielectric layer has a dielectric constant of about 100, the dielectric layer has an equivalent silicon dioxide thickness of from 4.0 to 7.0 Angstroms, and the second plurality comprises a material selected from the list including samarium, europium, gadolinium, holmium, erbium, thulium, dysprosium and neodymium oxides to form a nano-laminated dielectric layer.
 20. The electronic device of claim 19, wherein a first layer of titanium dioxide having a first selected thickness directly contacts a crystalline semiconductive substrate, a second layer of lanthanide oxide having a second selected thickness directly contact the first layer, and a selected number of alternating layers of titanium dioxide and lanthanide oxide provide a selected total dielectric thickness. 